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WO2013147291A1 - Capteur thermistor de type film - Google Patents

Capteur thermistor de type film Download PDF

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Publication number
WO2013147291A1
WO2013147291A1 PCT/JP2013/059797 JP2013059797W WO2013147291A1 WO 2013147291 A1 WO2013147291 A1 WO 2013147291A1 JP 2013059797 W JP2013059797 W JP 2013059797W WO 2013147291 A1 WO2013147291 A1 WO 2013147291A1
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WIPO (PCT)
Prior art keywords
film
thermistor
surface pattern
thin film
insulating film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2013/059797
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English (en)
Japanese (ja)
Inventor
長友　憲昭
寛 田中
均 稲場
賢治 久保田
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority to CN201380011410.XA priority Critical patent/CN104137196A/zh
Priority to US14/389,271 priority patent/US20150055682A1/en
Publication of WO2013147291A1 publication Critical patent/WO2013147291A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
    • G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
    • G01K7/226—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor using microstructures, e.g. silicon spreading resistance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K1/00—Details of thermometers not specially adapted for particular types of thermometer
    • G01K1/14—Supports; Fastening devices; Arrangements for mounting thermometers in particular locations
    • G01K1/143—Supports; Fastening devices; Arrangements for mounting thermometers in particular locations for measuring surface temperatures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/14—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
    • H01C1/142—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors the terminals or tapping points being coated on the resistive element
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/008—Thermistors

Definitions

  • the present invention relates to a film type thermistor sensor suitable as a temperature sensor that can be surface-mounted on a substrate.
  • a thermistor material used for a temperature sensor or the like is required to have a high B constant for high accuracy and high sensitivity.
  • transition metal oxides such as Mn, Co, and Fe are generally used for such thermistor materials (see Patent Documents 1 and 2).
  • these thermistor materials require firing at 600 ° C. or higher in order to obtain stable thermistor characteristics.
  • This Ta—Al—N-based material is produced by performing sputtering in a nitrogen gas-containing atmosphere using a material containing the above elements as a target. Further, the obtained thin film is heat-treated at 350 to 600 ° C. as necessary.
  • a very thin thermistor sensor can be obtained by using a film.
  • a thermistor material layer and an electrode layer are laminated on the film surface, and the electrical connection between the temperature sensor and an external circuit or the like is performed on the electrode layer on the film surface. This is done through lead wires connected by soldering.
  • this connection structure has a disadvantage that the temperature sensor cannot be directly mounted on the substrate and electrically connected.
  • a film made of a resin material generally has a heat resistant temperature as low as 150 ° C.
  • a polyimide known as a material having a relatively high heat resistant temperature has only a heat resistance of about 200 ° C.
  • the conventional oxide thermistor material requires firing at 600 ° C. or higher in order to realize desired thermistor characteristics, and there is a problem that a film type thermistor sensor directly formed on a film cannot be realized. Therefore, it is desired to develop a thermistor material that can be directly film-formed without firing, but even with the thermistor material described in Patent Document 3, the obtained thin film can be obtained as necessary in order to obtain desired thermistor characteristics. It was necessary to perform heat treatment at 350 to 600 ° C.
  • thermistor material a material having a B constant of about 500 to 3000 K is obtained in the example of the Ta-Al-N-based material, but there is no description regarding heat resistance, and the thermal reliability of the nitride-based material. Sex was unknown.
  • the present invention has been made in view of the above-described problems, and an object thereof is to provide a film type thermistor sensor which can be surface-mounted and can be directly formed on a film without firing.
  • the film-type thermistor sensor according to the first invention includes an insulating film, a thin film thermistor portion formed on the surface of the insulating film, and a pair of opposed electrode portions opposed to each other on the thin film thermistor portion.
  • the front surface pattern electrode and the back surface pattern electrode are electrically connected to each other through a via hole formed in a penetrating state in the insulating film.
  • the thin film-type thermistor sensor since the front surface pattern electrode and the back surface pattern electrode are electrically connected to the insulating film in which the thin film thermistor portion is formed through the via hole formed in the penetrating state, the circuit board By directly mounting on the surface, etc., the back surface pattern electrode or the front surface pattern electrode becomes a terminal portion and electrical connection is possible. Therefore, the thin film-type thermistor sensor that can be mounted on the surface speeds up the responsiveness of temperature measurement, and can also be mounted in a narrow space under an IC mounted on a circuit board or the like. This also makes it possible to directly measure the temperature of the IC directly under the IC.
  • the surface pattern electrode and back surface pattern electrode which become a terminal part are formed in the front and back, it can mount on the surface without distinguishing front and back. At this time, even if it is mounted on either side of the front and back surfaces, since a thin insulating film is used, a difference in response is unlikely to occur. Furthermore, since the front surface pattern electrode and the back surface pattern electrode are connected via the via hole, the insulating film and the front surface pattern electrode or the back surface pattern electrode are difficult to peel off during solder mounting due to the anchor effect.
  • the via hole anchor effect not only in the electrical connection to the back side via via holes used in semiconductor technology, but also in bent and bent states As a result, an effect peculiar to a film type sensor that the occurrence of cracks and peeling can be suppressed can be obtained.
  • the film type thermistor sensor according to a second aspect of the present invention is the film type thermistor sensor according to the first aspect, wherein a plurality of the via holes are arranged for each of the front surface pattern electrodes and are formed at least near the corners of the front surface pattern electrode or the back surface pattern electrode. It is characterized by being. That is, in this film type thermistor sensor, a plurality of via holes are arranged for each front surface pattern electrode, and at least near the corner of the front surface pattern electrode or back surface pattern electrode, a higher anchor effect can be obtained. In particular, it is possible to improve the adhesive strength in the vicinity of the corners of the pattern electrode where peeling easily occurs.
  • a film type thermistor sensor is characterized in that, in the first or second aspect of the invention, the film type thermistor sensor includes a protective film laminated on the thin film thermistor portion and formed of a resin.
  • this film type thermistor sensor is equipped with a protective film that is laminated on the thin film thermistor and formed of resin, so it can be mounted when the surface side of the insulating film faces the substrate or under the IC. Even in this case, the thin film thermistor portion can be insulated from the substrate and the IC by the protective film.
  • the thin film thermistor portion is disposed between the insulating film and the protective film and is positioned at the approximate center in the thickness direction, there is almost no difference in response even when mounted without distinction between the front and back sides.
  • the inventors of the present invention focused on the AlN system among the nitride materials and made extensive research. As a result, it is difficult for AlN as an insulator to obtain optimum thermistor characteristics (B constant: about 1000 to 6000 K). For this reason, it was found that by replacing the Al site with a specific metal element that improves electrical conduction and having a specific crystal structure, a good B constant and heat resistance can be obtained without firing.
  • the film type thermistor sensor of the present invention By using a material that has a hexagonal wurtzite type single phase and has a crystal structure, a good B constant can be obtained without firing, and high heat resistance can be obtained. Therefore, according to the film type thermistor sensor of the present invention, it is thin, flexible and excellent in responsiveness, and can be surface-mounted in various places such as under an IC mounted on a circuit board in a portable device, etc. Temperature measurement becomes possible.
  • 1st Embodiment of the film type thermistor sensor which concerns on this invention, it is sectional drawing, a top view, and a back view which show a film type thermistor sensor.
  • it is a Ti-Al-N type
  • it is sectional drawing and a top view which show the formation process of a thin film thermistor part.
  • 1st Embodiment it is sectional drawing, the top view, and back view which show the formation process of an electrode layer and a via hole. In 1st Embodiment, it is sectional drawing, the top view, and back view which show the pattern formation process of a dry film. In 1st Embodiment, it is sectional drawing, the top view, and back view which show the pattern formation process of a pattern electrode. In 1st Embodiment, it is sectional drawing and a top view which show the pattern formation process of a protective film. In 1st Embodiment, it is sectional drawing and a top view which show the via filling process by Cu plating.
  • Example which concerns on this invention it is a graph which shows the relationship between Al / (Ti + Al) ratio and B constant which compared the Example with strong a-axis orientation, and the Example with strong c-axis orientation.
  • it is a cross-sectional SEM photograph which shows an Example with strong c-axis orientation.
  • it is a cross-sectional SEM photograph which shows an Example with a strong a-axis orientation.
  • the film-type thermistor sensor 1 of the first embodiment includes an insulating film 2, a thin film thermistor portion 3 formed on the surface of the insulating film 2, and a pair of counter electrode portions facing each other.
  • a pair of back surface pattern electrodes 5 formed and a protective film 6 laminated on the thin film thermistor portion 3 and formed of resin are provided.
  • the said surface pattern electrode 4 and the back surface pattern electrode 5 are electrically connected through the via hole 2a formed in the insulating film 2 in the penetration state.
  • the insulating film 2 is formed in a band shape with, for example, a polyimide resin sheet.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate, or the like may be used.
  • the thin film thermistor portion 3 is formed of a TiAlN thermistor material.
  • the front surface pattern electrode 4 and the back surface pattern electrode 5 have a Cr or NiCr bonding layer and an electrode layer formed of Cu, Au or the like on the bonding layer.
  • the pair of surface pattern electrodes 4 are formed on the thin film thermistor portion 3 and are opposed to each other.
  • the counter electrode portion 4a is a pair of comb-shaped electrode portions arranged in opposition to each other, and an insulating film connected to the counter electrode portion 4a. 2 and a pair of surface terminal portions 4b formed on the surfaces of both end portions.
  • the pair of back surface pattern electrodes 5 are formed in a substantially rectangular pattern on the back surface of the insulating film 2 at positions facing the pair of front surface terminal portions 4b.
  • the via hole 2 a is formed in the center of the back pattern electrode 5.
  • the protective film 6 is, for example, formed of a polyimide resin and patterned in a rectangular shape larger than the thin film thermistor portion 3.
  • each composition ratio (x, y, z) (atomic%) of the points A, B, C, and D is A (15, 35, 50), B (2.5, 47.5, 50), C (3, 57, 40), D (18, 42, 40).
  • the thin film thermistor portion 3 is a columnar crystal formed in a film shape and extending in a direction perpendicular to the surface of the film. Further, it is preferable that the c-axis is oriented more strongly than the a-axis in the direction perpendicular to the film surface. Whether the a-axis orientation (100) is strong or the c-axis orientation (002) is strong in the direction perpendicular to the film surface (film thickness direction) is determined using X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • the manufacturing method of the film type thermistor sensor 1 includes a thin film thermistor portion forming step of patterning the thin film thermistor portion 3 on the insulating film 2, and a pair of through holes 2b serving as via holes 2a in the insulating film 2.
  • a step of forming a metal film on the inner surface of these through holes 2b to form via holes 2a, a pair of opposed electrode portions 4a facing each other on the thin film thermistor portion 3, and the surface of the insulating film 2 Forming a pair of front surface pattern electrodes 4 and forming a pair of back surface pattern electrodes 5 on the back surface, forming a protective film 6 on the thin film thermistor portion 3, and forming metal in the via hole 2a. And filling with a process.
  • a Ti-Al alloy sputtering target is used on the surface of the insulating film 2 of a rectangular polyimide film having a thickness of 25 ⁇ m, and Ti is formed by reactive sputtering in a nitrogen-containing atmosphere.
  • the sputtering conditions at that time were an ultimate vacuum of 5 ⁇ 10 ⁇ 6 Pa, a sputtering gas pressure of 0.4 Pa, a target input power (output) of 200 W, and a nitrogen gas fraction in an Ar gas + nitrogen gas mixed gas atmosphere. Fabricate at 20%.
  • a resist solution is applied on the top with a bar coater, prebaked at 110 ° C. for 1 minute and 30 seconds, exposed to light with an exposure device, then unnecessary portions are removed with a developer, and patterning is performed by post baking at 150 ° C. for 5 minutes. I do. Thereafter, an unnecessary thermistor material layer is wet-etched with a commercially available Ti etchant, and a thin film thermistor portion 3 of 0.8 ⁇ 0.8 mm is formed by resist stripping.
  • the square-shaped thin film thermistor part 3 is formed in the center of the surface of the insulating film 2.
  • the thin film thermistor portion 3 is hatched.
  • a through hole 2b having a diameter of 25 ⁇ m is formed by a YAG laser at the center of a region where the terminal portion (back surface pattern electrode 5) of the insulating film 2 is to be formed.
  • a Cr film of 20 nm is formed on both surfaces of the insulating film 2 by a sputtering method, and a Cu film is further formed to a thickness of 100 nm to form a Cr / Cu film 7.
  • a Cr film and a Cu film are continuously formed from the front and rear surfaces in a laminated state to form a via hole 2a.
  • the Cr / Cu film 7 is hatched.
  • a commercially available dry film 8 is formed on both surfaces of the Cu film on both sides of the insulating film 2 by thermocompression bonding at 110 ° C. Further, after exposure with an exposure apparatus, unnecessary portions are removed with a commercially available developer, and unnecessary electrode portions are wet-etched in the order of commercially available Cu etchant and Cr etchant.
  • the dry film 8 is hatched. Further, the dry film 8 is removed with a commercially available stripping solution, and the surface pattern electrode 4 composed of the counter electrode portion 4a and the surface terminal portion 4b is formed on the surface of the insulating film 2 as shown in FIG.
  • the back surface pattern electrode 5 connected to the front surface terminal portion 4b through the via hole 2a is patterned on the back surface of the insulating film 2.
  • a polyimide resin is screen-printed so as to cover the thin film thermistor portion 3 and baked at 200 ° C. to form a polyimide resin protective film 6 having a thickness of 25 ⁇ m as shown in FIG. Furthermore, after removing the oxidation of the Cu surface of the front surface terminal portion 4b and the back surface pattern electrode 5 as the terminal portions on both surfaces of the insulating film 2 with an acid, as shown in FIG. 9, via holes 2a having a diameter of 25 ⁇ m are formed by electric field Cu plating. Fill with Cu. At that time, 10 ⁇ m of Cu plating is formed on the surface of the front surface terminal portion 4 b and the back surface pattern electrode 5.
  • Ni of 3 ⁇ m is formed on Cu of the front surface terminal portion 4 b and the back surface pattern electrode 5, and Sn of 5 ⁇ m is further formed thereon, as shown in FIG.
  • a Ni / Sn plating film 9 is formed as a surface layer of the back pattern electrode 5.
  • a plurality of film type thermistor sensors 1 When a plurality of film type thermistor sensors 1 are manufactured simultaneously, a plurality of thin film thermistor portions 3, a front surface pattern electrode 4, a back surface pattern electrode 5, a protective film 6 and the like are formed on a large sheet of an insulating film 2 as described above. After that, each film type thermistor sensor 1 is cut from the large sheet. In this way, for example, a surface-mount type film thermistor sensor 1 having a size of 2.0 ⁇ 1.2 mm and a thickness of 0.07 mm and having a terminal portion on both sides is obtained.
  • the front surface pattern electrode 4 and the back surface pattern electrode 5 pass through the insulating film 2 in which the thin film thermistor portion 3 is formed through the via hole 2a formed in a penetrating state. Therefore, the back surface pattern electrode 5 or the front surface pattern electrode 4 can be used as a terminal portion for electrical connection by directly mounting on the circuit board or the like. Therefore, the thin film-type thermistor sensor 1 that can be mounted on the surface speeds up the temperature measurement responsiveness, and can also be mounted in a narrow space under the IC mounted on a circuit board or the like. This also makes it possible to directly measure the temperature of the IC directly under the IC.
  • the via hole 2a is not only electrically connected to the back surface by a via hole used in semiconductor technology, but also in a bent or bent state. An effect peculiar to a film type sensor that the occurrence of cracking and peeling can be suppressed by the anchor effect can be obtained.
  • the surface mounting can be performed without distinction between the front and back surfaces.
  • the thin insulating film 2 is used regardless of which side of the front and back surfaces is mounted, a difference in response is unlikely to occur.
  • the front surface pattern electrode 4 and the back surface pattern electrode 5 are connected via the via hole 2a, the insulating film 2 and the front surface pattern electrode 4 or the back surface pattern electrode 5 are difficult to peel off due to the anchor effect during solder mounting.
  • the protective film 6 is formed of resin laminated on the thin film thermistor portion 3, even when the surface side of the insulating film 2 is surface-mounted toward the substrate or mounted under the IC, The thin film thermistor portion 3 can be insulated from the substrate and IC by the protective film 6.
  • the thin film thermistor portion 3 is disposed between the insulating film 2 and the protective film 6 and is positioned at the approximate center in the thickness direction, there is almost no difference in response even when mounted without distinction between the front and back sides.
  • the film is formed by reactive sputtering in a nitrogen-containing atmosphere using a Ti—Al alloy sputtering target, the above-mentioned TiAlN is used.
  • the metal nitride material can be formed without firing. Further, by setting the sputtering gas pressure in reactive sputtering to less than 0.67 Pa, a metal nitride material film in which the c-axis is oriented more strongly than the a-axis in the direction perpendicular to the film surface is formed. be able to.
  • the thin film thermistor portion 3 is formed of the thermistor material layer on the insulating film 2, the thin film thermistor is formed by non-firing and has a high B constant and high heat resistance.
  • the part 3 can use the insulating film 2 having a low heat resistance such as a resin film, and a thin and flexible thermistor sensor having good thermistor characteristics.
  • substrate materials using ceramics such as alumina are often used in the past. For example, when the thickness is reduced to 0.1 mm, the substrate material is very brittle and easily broken. Therefore, for example, a very thin film type thermistor sensor having a thickness of 0.1 mm or less can be obtained.
  • the difference between the second embodiment and the first embodiment is that, in the first embodiment, one via hole 2a is provided for one surface pattern electrode 4, whereas the film type of the second embodiment.
  • a plurality of via holes 2 a are provided for each surface pattern electrode 4, and are formed at least near the corners of the surface pattern electrode 4 or the back surface pattern electrode 5.
  • each front surface pattern electrode 4 five via holes 2a are provided for each front surface pattern electrode 4, and one via hole 2a is formed at the center of the front surface terminal portion 4b and the back surface pattern electrode 5, and at these four corners.
  • a plurality of via holes 2a are arranged for each front surface pattern electrode 4, and are formed at least near the corners of the front surface pattern electrode 4 or the back surface pattern electrode 5.
  • a transition metal oxide (MnCoNi-based) thin film thermistor portion is formed on an alumina film having a thickness of 0.5 mm, and solder plating is applied to the terminal portion, thereby obtaining 2.0 ⁇ 1.2 ⁇ .
  • a 0.07 mm thin film thermistor chip was produced.
  • it was solder-mounted on a glass epoxy substrate having a thickness of 0.8 mm, and the deflection test was performed in the same manner as in the above example.
  • the thin film thermistor chip was cracked in the comparative example, whereas in this example, there was no problem in appearance without cracking or peeling, and both the resistance value change rate and the B constant change rate were 0.1% or less.
  • the electrical characteristics were also good.
  • a film evaluation element 121 shown in FIG. 11 was produced as follows. First, by reactive sputtering, Ti—Al alloy targets having various composition ratios are used to form Si substrates S on a Si wafer with a thermal oxide film at various composition ratios shown in Table 1 having a thickness of 500 nm. A thin film thermistor portion 3 of the formed metal nitride material was formed.
  • the sputtering conditions at that time were: ultimate vacuum: 5 ⁇ 10 ⁇ 6 Pa, sputtering gas pressure: 0.1 to 1 Pa, target input power (output): 100 to 500 W, and in a mixed gas atmosphere of Ar gas + nitrogen gas The nitrogen gas fraction was changed to 10 to 100%.
  • a 20 nm Cr film was formed on the thin film thermistor portion 3 by sputtering, and a 200 nm Au film was further formed. Furthermore, after applying a resist solution thereon with a spin coater, pre-baking is performed at 110 ° C. for 1 minute 30 seconds, and after exposure with an exposure apparatus, unnecessary portions are removed with a developing solution, and post baking is performed at 150 ° C. for 5 minutes. Patterning. Thereafter, unnecessary electrode portions were wet-etched with a commercially available Au etchant and Cr etchant, and a patterned electrode 124 having a desired comb-shaped electrode portion 124a was formed by resist stripping.
  • the X-ray source is MgK ⁇ (350 W)
  • the path energy is 58.5 eV
  • the measurement interval is 0.125 eV
  • the photoelectron extraction angle with respect to the sample surface is 45 deg
  • the analysis area is about Quantitative analysis was performed under the condition of 800 ⁇ m ⁇ .
  • the quantitative accuracy the quantitative accuracy of N / (Ti + Al + N) is ⁇ 2%
  • the quantitative accuracy of Al / (Ti + Al) is ⁇ 1%.
  • B constant (K) ln (R25 / R50) / (1 / T25-1 / T50)
  • R25 ( ⁇ ) resistance value at 25 ° C.
  • T25 (K): 298.15K 25 ° C. is displayed as an absolute temperature
  • T50 (K): 323.15K 50 ° C. is displayed as an absolute temperature
  • the Ti x Al y N 3 ternary triangular diagram of the composition ratio shown in FIG. 2 of z, the points A, B, C, in a region surrounded by D, ie, "0.70 ⁇ y / (x + y) ⁇ 0.95, 0.4 ⁇ z ⁇ 0.5, x + y + z 1 ”, thermistor characteristics of resistivity: 100 ⁇ cm or more, B constant: 1500 K or more Has been achieved.
  • FIG. 12 shows a graph showing the relationship between the resistivity at 25 ° C. and the B constant from the above results.
  • a high resistance and high B constant region having a specific resistance value at 25 ° C. of 100 ⁇ cm or more and a B constant of 1500 K or more can be realized.
  • the B constant varies for the same Al / (Ti + Al) ratio because the amount of nitrogen in the crystal is different.
  • Comparative Examples 3 to 12 shown in Table 1 are regions of Al / (Ti + Al) ⁇ 0.7, and the crystal system is cubic NaCl type.
  • the NaCl type and the wurtzite type coexist.
  • the specific resistance value at 25 ° C. was less than 100 ⁇ cm
  • the B constant was less than 1500 K
  • the region was low resistance and low B constant.
  • Comparative Examples 1 and 2 shown in Table 1 are regions where N / (Ti + Al + N) is less than 40%, and the metal is in a crystalline state with insufficient nitriding.
  • Comparative Examples 1 and 2 neither the NaCl type nor the wurtzite type was in a state of very poor crystallinity. Further, in these comparative examples, it was found that both the B constant and the resistance value were very small and close to the metallic behavior.
  • Thin film X-ray diffraction (identification of crystal phase)
  • the crystal phase of the thin film thermistor portion 3 obtained by the reactive sputtering method was identified by grazing incidence X-ray diffraction (Grazing Incidence X-ray Diffraction).
  • the impurity phase is not confirmed, and is a wurtzite type single phase.
  • the crystal phase was neither the wurtzite type phase nor the NaCl type phase as described above, and could not be identified in this test. Further, these comparative examples were materials with very poor crystallinity because the peak width of XRD was very wide. This is considered to be a metal phase with insufficient nitriding because it is close to a metallic behavior due to electrical characteristics.
  • all the examples of the present invention are films of wurtzite type phase, and since the orientation is strong, is the a-axis orientation strong in the crystal axis in the direction perpendicular to the Si substrate S (film thickness direction)? Whether the c-axis orientation is strong was investigated using XRD. At this time, in order to investigate the orientation of the crystal axis, the peak intensity ratio between (100) (Miller index indicating a-axis orientation) and (002) (Miller index indicating c-axis orientation) was measured.
  • the example in which the film was formed at a sputtering gas pressure of less than 0.67 Pa was a film having a (002) strength much stronger than (100) and a stronger c-axis orientation than a-axis orientation.
  • the example in which the film was formed at a sputtering gas pressure of 0.67 Pa or higher was a material having a (100) strength much stronger than (002) and a a-axis orientation stronger than the c-axis orientation.
  • it formed into a film on the polyimide film on the same film-forming conditions it confirmed that the single phase of the wurtzite type phase was formed similarly.
  • orientation does not change.
  • FIG. 1 An example of the XRD profile of an example with strong c-axis orientation is shown in FIG.
  • Al / (Ti + Al) 0.84 (wurtzite type, hexagonal crystal), and the incident angle was 1 degree.
  • the intensity of (002) is much stronger than (100).
  • FIG. 1 An example of the XRD profile of an Example with a strong a-axis orientation is shown in FIG.
  • Al / (Ti + Al) 0.83 (wurtzite type, hexagonal crystal), and the incident angle was measured as 1 degree.
  • the intensity of (100) is much stronger than (002).
  • FIG. 1 An example of the XRD profile of the comparative example is shown in FIG.
  • Al / (Ti + Al) 0.6 (NaCl type, cubic crystal), and the incident angle was 1 degree.
  • a peak that could be indexed as a wurtzite type (space group P6 3 mc (No. 186)) was not detected, and it was confirmed to be a NaCl type single phase.
  • the correlation between the crystal structure and the electrical characteristics was further compared in detail for the example of the present invention which is a wurtzite type material.
  • a material in which the crystal axis having a high degree of orientation in the direction perpendicular to the substrate surface is the c-axis with respect to the Al / (Ti + Al) ratio being substantially the same ratio (Examples 5, 7, 8, 9) and a material which is a-axis (Examples 19, 20, 21).
  • the material having a strong c-axis orientation has a B constant of about 100K higher than that of a material having a strong a-axis orientation.
  • FIG. 18 shows a cross-sectional SEM photograph of the thin film thermistor portion 3 having a strong c-axis orientation.
  • the samples of these examples are those obtained by cleaving the Si substrate S. Moreover, it is the photograph which observed the inclination at an angle of 45 degrees.
  • the ionic radius of Ta is much larger than that of Ti or Al, so that a wurtzite phase cannot be produced in a high concentration Al region. Since the TaAlN system is not a wurtzite type phase, the Ti-Al-N system of the wurtzite type phase is considered to have better heat resistance.
  • the TiAlN thin film thermistor portion is preferable as described above, but a thin film thermistor portion formed of another thermistor material may be employed.
  • the surface pattern electrode (counter electrode portion) is formed on the thin film thermistor portion, the surface pattern electrode may be formed below the thin film thermistor portion.

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  • Thermistors And Varistors (AREA)

Abstract

L'invention concerne un capteur thermistor de type film qui peut être monté en surface et peut être directement formé sur un film, ou analogue, sans cuisson. Le capteur thermistor de type film comprend : un film isolant (2); une partie thermistor en couche mince (3) formée sur la surface supérieure du film isolant (2); une paire d'électrodes à motif de surface supérieure (4) dans lesquelles une paire de parties de contre-électrode (4a), qui se font face l'une avec l'autre, est disposée au-dessus ou au-dessous de la partie thermistor en couche mince (3), et est formée sur la surface supérieure du film isolant; et une paire d'électrodes à motif de surface inférieure (5) formée sur la surface inférieure du film isolant de façon à faire face à une partie de la paire d'électrodes à motif de surface supérieure. Les électrodes à motif de surface supérieure et les électrodes de surface inférieure sont connectées électriquement par l'intermédiaire de trous d'interconnexion (2a) formés de façon à pénétrer le film isolant.
PCT/JP2013/059797 2012-03-30 2013-03-25 Capteur thermistor de type film Ceased WO2013147291A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201380011410.XA CN104137196A (zh) 2012-03-30 2013-03-25 薄膜型热敏电阻传感器
US14/389,271 US20150055682A1 (en) 2012-03-30 2013-03-25 Film-type thermistor sensor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-081106 2012-03-30
JP2012081106A JP2013211433A (ja) 2012-03-30 2012-03-30 フィルム型サーミスタセンサ

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WO2013147291A1 true WO2013147291A1 (fr) 2013-10-03

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PCT/JP2013/059797 Ceased WO2013147291A1 (fr) 2012-03-30 2013-03-25 Capteur thermistor de type film

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US (1) US20150055682A1 (fr)
JP (1) JP2013211433A (fr)
CN (1) CN104137196A (fr)
TW (1) TWI555039B (fr)
WO (1) WO2013147291A1 (fr)

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JP6460376B2 (ja) * 2014-08-29 2019-01-30 三菱マテリアル株式会社 温度センサ及びその製造方法
CN105043575B (zh) * 2015-05-08 2017-08-25 国家海洋技术中心 一种高灵敏度薄膜型电阻温度传感器制造方法
CN106197726A (zh) * 2016-07-07 2016-12-07 安徽晶格尔电子有限公司 一种单面极ntc热敏芯片及其制备方法
CN106197725A (zh) * 2016-07-07 2016-12-07 安徽晶格尔电子有限公司 一种单面极热电阻温度传感器
CN108106750B (zh) * 2017-12-20 2020-05-19 肇庆爱晟传感器技术有限公司 一种薄片型温度传感器及其制备方法
JP7085378B2 (ja) * 2018-03-23 2022-06-16 Koa株式会社 チップ抵抗器
DE102018221551A1 (de) * 2018-12-12 2020-06-18 Robert Bosch Gmbh Sensor, elektrischer Energiespeicher und Vorrichtung
CN109540322B (zh) * 2018-12-29 2020-06-30 肇庆爱晟传感器技术有限公司 一种表面贴装快速反应耐高温温度传感器
JP7424785B2 (ja) * 2019-10-01 2024-01-30 日東電工株式会社 温度センサフィルム、導電フィルムおよびその製造方法
DE102019127915A1 (de) * 2019-10-16 2021-04-22 Tdk Electronics Ag Sensorelement und Verfahren zur Herstellung eines Sensorelements
DE102019127924B3 (de) * 2019-10-16 2021-01-21 Tdk Electronics Ag Bauelement und Verfahren zur Herstellung eines Bauelements
DE102020122923A1 (de) * 2020-09-02 2022-03-03 Tdk Electronics Ag Sensorelement und Verfahren zur Herstellung eines Sensorelements
CN116344128A (zh) * 2021-12-23 2023-06-27 国巨电子（中国）有限公司 表面粘着型电阻器及其制造方法
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JP2013211433A (ja) 2013-10-10
US20150055682A1 (en) 2015-02-26
TW201401306A (zh) 2014-01-01
TWI555039B (zh) 2016-10-21
CN104137196A (zh) 2014-11-05

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